Labile bromine fire suppressants

ABSTRACT

A class of fire suppressant compounds which have labile bromine atoms bound to atoms other than carbon have been discovered to be more effective at suppressing fires than Halon 1211 and Halon 1301. Moreover, this class of fire suppressant compounds hydrolyze or oxidize rapidly in the troposphere and as a consequence thereof, they have minimal ozone depletion potential.

Notice: More than one reissue application has been filed for the reissueof U.S. Pat. No. 5,626,786. The reissue applications are applicationSer. No. 10/893,705, application number not yet assigned, andapplication number not yet assigned (the present application), all ofwhich are divisional reissues of U.S. Pat. No. 5,626,786.

GOVERNMENT RIGHTS

This invention was made with support by the U.S. Government. TheGovernment may have certain rights in this invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to prevention and extinguishmentof fires combustible materials by utilizing a composition of mattergroup which is highly efficient and environmentally friendly. Moreparticularly, the invention relates to prevention and extinguishment offires of combustible materials by using a group of fire suppressantshaving labile bonds between bromine atoms and atoms other than carbon.

2. Description of the Prior Art

Fire suppression by halogenated alkanes is well-established in both thescientific literature and commercial practice as taught, for example, inR. G. Gann ed., Halogenated Fire Suppressants, ACS Symposium Series 16(American Chemical Society, Washington, D.C.) 1975. The two most widelyused halogenated suppressants are Halon 1301 (CF₃Br) and Halon 1211(CF₂ClBr). These compounds are very stable, so they survive long enoughin the troposphere to be gradually transported to the stratosphere,where they are photolyzed by solar ultraviolet radiation to produce freeradicals that catalyze ozone depletion as taught, for example, in J. G.Anderson, D. W. Toohey, and W. F. Brune, Science, 251, 39 (1991).Production of these materials has therefore been internationallyprohibited after January, 1994 by the Montreal Protocol on Substancesthat Deplete the Ozone Layer. The problem is therefore to find firesuppression materials and methods which are at least as effective asHalon 1301 and Halon 1211 but which do not deplete the ozone layer.

Representative of the prior art directed to the use of fluorocarbonswhich have no chlorine or bromine is U.S. Pat. No. 5,236,611 (Shiflet).These fluorocarbons are slowly transported into the stratosphere, butthe catalytic efficiency of fluorine is very much smaller than that ofchlorine, bromine, or iodine.

Representative of the prior art directed to the use of hydrogenatedhalocarbons, which are less stable than Halon 1301 or Halon 1211 in thetroposphere, are U.S. Pat. Nos. 5,084,190 (Fernandez), 5,135,054 (Nimitzet al.); 5,093,013 (Sprague); and 5,080,177 (Robin et al.). It is wellknown that Halons containing chlorine or bromine will suppress fires insmaller quantities than those which contain only fluorine. However, itis understood by people practiced in the art of combustion that theprincipal source of heat release in hydrocarbon combustion is oxidationof hydrogen atoms to form water vapor. Thus hydrogenated halocarbons areexpected to act chemically both as fuels and as fire suppressants.

SUMMARY OF THE INVENTION

In accordance with the teachings of the present invention compositionsof matter having labile bromine atoms bound to atoms other than carbonhave been discovered to have improved fire suppressant properties and tobe environmentally friendly. Compounds which release bromine atoms andare commonly used as brominating agents in organic synthesis such asphosphorus tribromide (PBr₃), thionyl bromide (SOBr₂), boron tribromide(BBr₃), and the like are very efficient at extinguishing fires.Moreover, they hydrolyze or oxidize rapidly in the troposphere andconsequently they have no stratospheric ozone depletion potential.

Additionally included in this class of fire suppressant compounds oflabile bromine atoms bound to atoms other than carbon are silicontetrabromide (SiBr₄), titanium tetra-bromide (TiBr₄), iodine bromide(TBr), phosphorous oxy-bromide (POBr₃), bromine trifluoride (BrF₃),bromine pentafluoride (BrF₅), N-bromosuccinimide (C₄H₄O₂NBr) {thebromine is bound to nitrogen, not carbon}, nitrosyl bromide (NOBr),chlorine bromide (ClBr), and cuprous bromide (CuBr). These compounds areused as brominating agents in chemical synthesis as taught, for example,in the Merck Index, ninth edition, (Merck & Co., Rahway, N.J., 1976) orsuffer thermal decomposition with liberation of bromine at temperaturesless than 200 degrees centigrade.

Examples of non-labile bromine compositions are found in suchhigh-melting, ionically bound salts as lithium bromide (LiBr, m.p. 547°C.), calcium bromide (CaBr₂, m.p. 730° C.), or chromous bromide (CrBr₂,m.p. 842° C.), and other bromine-containing compositions that arethermally and oxidatively stable according to criteria familiar topeople practiced in the art of synthetic chemistry.

In order to extinguish fires with a composition having one or morecompounds of the aforesaid class of fire suppressants, equipment fordelivering the composition incorporates such factors as specificgeometry, gas flow, and flame conditions. A method of delivery of acomposition having one or more liquid compounds of the aforesaid classof fires suppressants may employ a nonflammable, pressurized gas topropel the composition through a nozzle to the flame. Another method ofdelivery of liquid compositions may employ a deflagrating solid,gas-generating cartridge, such as is found in automotive airbags, topropel a mist of liquid to the flame. A third method for delivery ofliquid compositions may employ a pressurized liquid propellant such asliquid carbon dioxide or liquid argon to atomize and direct a mist ofsuppressant onto the flame. Other methods for propelling powders orslurries of solid materials of the aforesaid class may employ adeflagrating solid gas generating cartridge and a wider nozzle such aswould be used for an ordinary shotgun cartridge. Other methods forpropelling gaseous materials of the aforesaid class may employ mixtureswith pressurized inert propellants to aid transport of suppressant tothe flame.

The primary advantage of the use of the class of fire suppressants ofthis discovery is to extinguish fires more efficiently with smallervolumes and masses of extinguishant than existing fire suppressants,without depleting the stratospheric ozone layer. PBr₃, POBr₃, SOBr₂,BBr₃, and the like react rapidly with water vapor or liquid to producemild acids which precipitate with normal rain and are ultimatelyneutralized in soils. The short lifetimes of these materials also reducetoxicity of the suppressants since their simple acid decompositionproducts pose no chronic risk to pH buffered, living organisms.

These and other advantages and attainments of the present invention willbecome apparent to those skilled in the art upon a reading of thedetailed description wherein there are described several embodiments ofthe invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the teachings of the present invention a class offire suppressants which have labile bromine atoms bound to atoms otherthan carbon are shown in Table I. These compounds are more effective atsuppressing fire than Halon 1301 or Halon 1211 and have no ozonedepletion potential.

The effectiveness of the class of suppressants described herein is aresult of the relative ease with which bromine atoms are liberated in aflame environment. Halons 1301 and 1211 also liberate bromine atoms in aflame; however, the strength of the C—Br bond in these materialsrequires higher temperatures or longer interaction times than thecompositions of matter described herein. The stability of the Halonsagainst oxidation or hydrolysis in the troposphere is one indication ofthe stability of the C—Br bond. The compositions of matter describedherein are not stable in the presence of water, oxygen, or heat,liberating bromine atoms under these conditions and thereby providing acatalyst for flame suppression.

Another indication of the stability of the C—Br bond is the measurementof its bond dissociation energy of 68 kilocalories per mole as taught byA. H. Sehon and M. Szware (Proceedings of the Royal Society (London),page 110, [1951]). This energy is larger than the bond energy of typicalP—Br bonds (63 kcal/mole), I—Br bonds (43 kcal/mole), or S—Br bonds (52kcal/mole) as taught by Streitweiser and Heathcock, Introduction toOrganic Chemistry, (Macmillan:NY), 1976 and Cotton and Wilkinson,Advanced Inorganic Chemistry, (3rd ed. Wiley:NY), 1972. As is known topeople practiced in the art of chemistry the interpretation of bonddissociation energies involves approximations based on the nature of thefull molecular fragments (XY_(n)) from which bromine is liberatedaccording to the reaction:Y_(n)X—Br→Y_(n)X+Br.Thus lower average bond energies indicate the possibility of labilebonds in a group of materials, but further experimentation with specificmaterials is required to establish the lability of the bond comparedwith Halons.

TABLE I Composition Phase % Br Comments PBr₃ liquid 88 brominating agentPOBr₃ liquid 83 brominating agent SOBr₂ liquid 77 brominating agent BrF₃liquid 58 reactive solvent BrF₅ liquid 46 reactive solvent PBr₅ solid 92brominating agent TiBr₄ solid 87 reacts with water SiBr₄ liquid 92reacts with water IBr solid 39 decomposes at 116° C. CuBr solid 29brominating agent NOBr gas 73 brominating agent BrF gas 81 boils at −20°C. C₄H₄O₂NBr solid 44.9 decomposes at 170° C. BBr₃ liquid 96 boils at90° C. BrCl gas 70 decomposes at 10° C.

In one embodiment of the invention liquid SOBr₂ is introduced as anair-pressurized mist into a 500,000 Btu/hr fire resulting from keroseneflowing at a rate of 4 grams per second through a nozzle withcross-flowing compressed air to atomize the liquid into a fine mist. Thefire is contained in a flame holder whose volume is approximately 8liters and is further blown by an atmospheric cross-wind of 40 miles perhour. The fire is reproducibly and irreversibly extinguished with lessthan one gram of SOBr₂ in less than 0.2 seconds as confirmed byvideotape records of the experiments. The same fire is not reproduciblysuppressed with aliquots of 25 grams of CF₃Br added to the samelocation.

In another embodiment of the invention 0.2 cubic centimeters of PBr₃ ismixed with 0.7 cubic centimeters of liquid carbon dioxide. The liquidCO₂ propels the PBr₃ through a valve and into the flame zone, generatedas herein above described, as it is opened, irreversibly and completelyextinguishing the flame in the presence of flowing fuel, air, and hotsurfaces.

Extinguishment of a similar fire, with a hydrocarbon fuel burn rate of12 grams per second, by Halon 1301 is taught by Alvarez in chapter 3 ofGann (ibid.) to require between 90 and 130 grams per second of CF₃Br forsuppression. Another example of a gasoline fire with similar heat outputis taught by Ford in chapter 1 of Gann (ibid.) to require between 500and 1500 grams of Halon 1301 for suppression. Another fire, in which 10grams per second of jet fuel are burned in fast-flowing air at the AirForce Flight Dynamics Laboratory Engine Nacelle test facility(Wright-Patterson AFB, OH) requires between one and three kilograms ofHalon 1301 for reproducible suppression. In each of these examples thequantity of Halon 1301 required to suppress a similar fire is between100 and 1000 times greater than that required of the compositions ofmatter described herein above, of which SOBr₂ and PBr₃ are specificembodiments.

The labile bromine atoms and high proportion of bromine in thecomposition of matter listed in Table I provide a more efficient firesuppression formulation than the Halons, which typically have lessbromine by weight (Halon 1301 and 1211 are 54% and 48% Br, respectively)and lesser proclivity for liberating bromine atoms when thermally orchemically activated in a combustion environment.

Methods for dispersing gas, liquid, or solid suppressants requiredesigns based upon such factors as specific geometry of the locus of thefire, flow properties of the fire suppressants, and flame conditions ofthe fire. For example, fine mists of liquid are transported byfluid-dynamical drag forces along flow streamlines in the nacelle of anaircraft engine. The mists vaporize in hot zones, liberating bromineatoms by pyrolysis in precisely the regions where the heat released bycombustion is most intense. Inasmuch as the drag coefficient isinversely proportional to the droplet diameter, as is known to peoplepracticed in the art of fluid dynamics, there is a range of aerosol sizedistributions which most effectively deliver specific suppressants tospecific fires. Another such factor for a gaseous composition is themixing of suppressant flow with turbulent flames in a well-ventilatedfire, which is affected by the delivery pressure, the nozzle contour andorientation, the mass-flow rate of the suppressant, and the fluiddynamical properties of the fire. Dispersing methods designed forsuppressing fire in the nacelle of a jet engine differ from dispersingmethods designed for suppressing fire in the engine compartment of amotor vehicle, the flu of a chimney, or the gas-handling manifold of asemiconductor processing clean-room.

Methods for preventing and extinguishing fires of jet fuel using acomposition of matter class which is highly efficient andenvironmentally friendly is also disclosed by the present inventors inFinal Technical Report FR-4021 (US Air Force Phase I SBIR ContractF33615-94-C-5005, November 1994).

Although preferred embodiments of the invention have been described, itwill be understood that within the scope of this invention variouschanges may be made in the amount of fire suppressant, the compositionof a fire suppressant mixture, and the method for dispersing firesuppressants which is generally stated consist of a class of firesuppressants and methods of dispersing such fire suppressants capable ofcarrying out the objects set forth as disclosed in the appended claims.

1. A fire suppressant composition consisting essentially of at least onebrominated, non-carbon compound selected from the group consisting ofPBr₃, POBr₃, SOBr₂, BrF₃, BrF₅, PBr₅, TiBr₄, SiBr₄, IBr, CuBr, NOBr,BrF, and BBr₃, which is combined with a propellant such that the ozonedepletion potential of the composition is less than 0.1.
 2. The firesuppressant composition of claim 1 wherein ozone depletion potential isdefined on a scale where the ozone depletion caused by CFI₃ is 1.0.
 3. Afire suppressant composition consisting of at least one labilebrominated compound selected from the group consisting of PBr₃, POBr₃,SOBr₂, BrF₃, BrF₅, TiBr₄, SiBr₄, IBr, CuBr, NOBr, BrF, BBr₃, and BrCl,which is combined with a propellant selected from the group consistingof CO₂, N₂, compressed air, and HCFC-123 (CF₃CCl₂H).
 4. The firesuppressant composition of claim 3 wherein ozone depletion potential ofthe propellant equals 0.016.
 5. A fire suppressant compositionconsisting essentially of: at least one brominated, non-carbon compoundin a liquid state selected from the group consisting of TiBr ₄ and SiBr₄ ; and a propellant combined with the compound for propelling thecomposition such that sufficient bromine atoms are liberated from thecomposition to suppress a fire, wherein the composition has no ozonedepletion potential.
 6. The composition of claim 5, wherein thepropellant is selected from the group consisting of CO₂ , N ₂ , andcompressed air.
 7. The composition of claim 5 wherein said brominatedcompound is TiBr₄ .
 8. The composition of claim 5 wherein saidbrominated compound is SiBr₄ .
 9. The composition of claim 5 whereinsaid brominated compound is TiBr₄ and the propellant is nonflammable.10. The composition of claim 5 wherein said brominated compound is SiBr₄and the propellant is nonflammable.
 11. The composition of claim 7wherein said brominated compound is not stable in, and said sufficientbromine atoms are liberated in, the presence of oxygen.
 12. Thecomposition of claim 11 wherein said liberated bromine atoms aresufficient to catalytically suppress the fire.
 13. The composition ofclaim 7 wherein said brominated compound is not stable in, and saidsufficient bromine atoms are liberated in, the presence of heat.
 14. Thecomposition of claim 13 wherein said liberated bromine atoms aresufficient to catalytically suppress the fire.
 15. The composition ofclaim 7 wherein said brominated compound is not stable in, and saidsufficient bromine atoms are liberated in, the presence of water. 16.The composition of claim 15 wherein said wherein said liberated bromineatoms are sufficient to catalytically suppress the fire.
 17. Thecomposition of claim 8 wherein said brominated compound is not stablein, and said sufficient bromine atoms are liberated in, the presence ofoxygen.
 18. The composition of claim 17 wherein said liberated bromineatoms are sufficient to catalytically suppress the fire.
 19. Thecomposition of claim 8 wherein said brominated compound is not stablein, and said sufficient bromine atoms are liberated in, the presence ofheat.
 20. The composition of claim 19 wherein said liberated bromineatoms are sufficient to catalytically suppress the fire.
 21. Thecomposition of claim 8 wherein said brominated compound is not stablein, and said sufficient bromine atoms are liberated in, the presence ofwater.
 22. The composition of claim 21 wherein said wherein saidliberated bromine atoms are sufficient to catalytically suppress thefire.
 23. The composition of claim 7 wherein the propellant is selectedfrom the group consisting of a non-flammable, pressurized gas; adeflagrating, solid, gas-generating cartridge; and a pressurized liquid.24. The composition of claim 8 wherein the propellant is selected fromthe group consisting of a non-flammable, pressurized gas; adeflagrating, solid, gas-generating cartridge; and a pressurized liquid.25. A fire suppressant composition consisting essentially of TiBr₄ in aliquid state and a propellant combined with the TiBr ₄ for propellingthe composition to catalytically suppress a fire, wherein thecomposition has no ozone depletion potential.
 26. The composition ofclaim 25, wherein the propellant is selected from the group consistingof CO₂ , N ₂ , and compressed air.
 27. The composition of claim 25wherein the propellant is nonflammable.
 28. The composition of claim 25wherein the TiBr₄ is not stable in the presence of at least one ofoxygen, heat, and water.
 29. The composition of claim 25 wherein thepropellant is selected from the group consisting of a non-flammable,pressurized gas; a deflagrating, solid, gas-generating cartridge; and apressurized liquid.
 30. A fire suppressant composition consistingessentially of SiBr₄ in a liquid state and a propellant combined withthe SiBr ₄ for propelling the composition to catalytically suppress afire, wherein the composition has no ozone depletion potential.
 31. Thecomposition of claim 30, wherein the propellant is selected from thegroup consisting of CO₂ , N ₂ , and compressed air.
 32. The compositionof claim 30 wherein the propellant is nonflammable.
 33. The compositionof claim 30 wherein the SiBr₄ is not stable in the presence of at leastone of oxygen, heat, and water.
 34. The composition of claim 30 whereinthe propellant is selected from the group consisting of a non-flammable,pressurized gas; a deflagrating, solid, gas-generating cartridge; and apressurized liquid.